Synthesis and characterization of Ru alkylidene complexes

Abstract

This invention relates generally to olefin metathesis catalyst compounds, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, articles of manufacture comprising such compounds, and the use of such compounds in the metathesis of olefins and olefin compounds. The invention has utility in the fields of catalysts, organic synthesis, polymer chemistry, and industrial and fine chemicals industry.

What is claimed is: 
     
       1. An olefin metathesis catalyst represented by Formula (I): 
       
         
           
           
               
               
           
         
         wherein:
 M is ruthenium or osmium; 
 X 1  and X 2  are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; 
 L 1  is a ligand represented by the structure of Formula (II), or is a N-Heterocyclic Carbene ligand represented by the structure of Formula (III): 
 
       
       
         
           
           
               
               
           
         
         
           R 1  is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C 1 -C 24  alkyl), —N(C 1 -C 24  alkyl) 2 , —NH(C 5 -C 24  aryl), —N(C 5 -C 24  aryl) 2 , —N(C 1 -C 24  alkyl)(C 5 -C 24  aryl) or —N[(C 1 -C 6  alkylene) (C 5 -C 24  aryl)] 2 ; 
           R 2  is unsubstituted (C 5 -C 24  aryl), substituted (C 5 -C 24  aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C 1 -C 24  alkyl), —N(C 1 -C 24  alkyl) 2 , —NH(C 5 -C 24  aryl), —N(C 5 -C 24  aryl) 2 , —N(C 1 -C 24  alkyl)(C 5 -C 24  aryl) or —N[(C 1 -C 6  alkylene)(C 5 -C 24  aryl)] 2 ; 
           R 3  is unsubstituted (C 5 -C 24  aryl), substituted (C 5 -C 24  aryl), unsubstituted saturated N-heterocycle, or substituted saturated N-heterocycle; 
           Y is CR 4  or N; 
           R 4  is hydrogen, unsubstituted (C 1 -C 12  alkyl), or substituted (C 1 -C 12  alkyl); 
           R 5  and R 6  are independently hydrogen, unsubstituted (C 5 -C 24  aryl), or substituted (C 5 -C 24  aryl); 
           Q is a two-atom linkage represented by structures —[CR 7 R 8 ] s —[CR 9 R 10 ] t — or —[CR 11 ═CR 12 ]—; 
           R 7 , R 8 , R 9  and R 10  are independently hydrogen, unsubstituted (C 1 -C 24  alkyl), substituted (C 1 -C 24  alkyl), unsubstituted (C 5 -C 24  aryl), or substituted (C 5 -C 24  aryl); 
           R 11  and R 12  are independently hydrogen, unsubstituted (C 1 -C 24  alkyl), substituted (C 1 -C 24  alkyl), unsubstituted (C 5 -C 24  aryl), or substituted (C 5 -C 24  aryl); and 
           “s” and “t” are independently 1 or 2. 
         
       
     
     
       2. The olefin metathesis catalyst according to  claim 1 , represented by the structure of Formula (VI): 
       
         
           
           
               
               
           
         
         wherein:
 X 1  is Cl; 
 X 2  is Cl; 
 R 1  is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; 
 R 2  is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and 
 R 3  is phenyl or morpholino. 
 
       
     
     
       3. The olefin metathesis catalyst according to  claim 2 , selected from: 
       
         
           
           
               
               
           
         
       
     
     
       4. The olefin metathesis catalyst according to  claim 1 , represented by the structure of Formula (VII): 
       
         
           
           
               
               
           
         
       
     
     
       5. The olefin metathesis catalyst according to  claim 4 , represented by the structure of Formula (VIII): 
       
         
           
           
               
               
           
         
         wherein:
 X 1  is Cl; 
 X 2  is Cl; 
 R 1  is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; 
 R 2  is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; 
 R 3  is phenyl or morpholino; and 
 R 5  and R 6  are independently 2,4,6-trimethyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propylphenyl or 2-methyl-6-iso-propylphenyl; 
 Q is a two-atom linkage represented by structure —[CR 7 R 8 ] s —[CR 9 R 10 ] t —; 
 R 7 , R 8 , R 9  and R 10  are independently hydrogen; and 
 “s” and “t” are independently 1. 
 
       
     
     
       6. The olefin metathesis catalyst according to  claim 5 , selected from: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
       7. A method of synthesizing an olefin metathesis catalyst represented by the structure of Formula (A): 
       
         
           
           
               
               
           
         
         the method comprising contacting an olefin metathesis catalyst represented by the structure of Formula (VIII): 
       
       
         
           
           
               
               
           
         
         with a PR d R e OR f  ligand at room temperature in an inert solvent, wherein:
 X 1  and X 2  are independently halogen, trifluoroacetate, per-fluorophenols or nitrate; 
 R 1  is unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C 1 -C 24  alkyl), —N(C 1 -C 24  alkyl) 2 , —NH(C 5 -C 24  aryl), —N(C 5 -C 24  aryl) 2 , —N(C 1 -C 24  alkyl)(C 5 -C 24  aryl) or —N[(C 1 -C 6  alkylene)(C 5 -C 24  aryl)] 2 ; 
 R 2  is unsubstituted (C 5 -C 24  aryl), substituted (C 5 -C 24  aryl), unsubstituted saturated N-heterocycle, substituted saturated N-heterocycle, —NH(C 1 -C 24  alkyl), —N(C 1 -C 24  alkyl) 2 , —NH(C 5 -C 24  aryl), —N(C 5 -C 24  aryl) 2 , —N(C 1 -C 24  alkyl)(C 5 -C 24  aryl) or —N[(C 1 -C 6  alkylene)(C 5 -C 24  aryl)] 2 ; 
 R 3  is unsubstituted (C 5 -C 24  aryl), substituted (C 5 -C 24  aryl), unsubstituted saturated N-heterocycle or substituted saturated N-heterocycle; 
 R 5  and R 6  are independently hydrogen, unsubstituted C 5 -C 24  aryl, or substituted C 5 -C 24  aryl; generally R 5  and R 6  are independently substituted C 5 -C 24  aryl with one to three unsubstituted (C 1 -C 6  alkyl) groups or substituted (C 1 -C 6  alkyl) groups; 
 R d  is unsubstituted C 1 -C 10  alkyl, substituted C 1 -C 10  alkyl, substituted C 6 -C 10  aryl, unsubstituted C 6 -C 10  aryl, substituted C 3 -C 8  cycloalkyl or unsubstituted C 3 -C 8  cycloalkyl; 
 R e  is unsubstituted C 1 -C 10  alkyl, substituted C 1 -C 10  alkyl, substituted C 6 -C 10  aryl, unsubstituted C 6 -C 10  aryl, substituted C 3 -C 8  cycloalkyl or unsubstituted C 3 -C 8  cycloalkyl; and 
 R f  is unsubstituted C 1 -C 10  alkyl, substituted C 1 -C 10  alkyl, substituted C 6 -C 10  aryl, unsubstituted C 6 -C 10  aryl, substituted C 3 -C 8  cycloalkyl or unsubstituted C 3 -C 8  cycloalkyl. 
 
       
     
     
       8. The method according to  claim 7 , wherein:
 X 1  is Cl; 
 X 2  is Cl; 
 R 1  is morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; 
 R 2  is phenyl, morpholino, thiomorpholino, 1-methyl-piperazino, piperidino, N-acetyl-piperazino, di-benzyl-amino, N-ethylcarboxylate-piperazino, diethylamino, methyl-phenylamino, or di-iso-propylamino; and
 R 3  is phenyl or morpholino 
 R 5  is 2,4,6-trimethylphenyl; 
 R 6  is 2,4,6-trimethylphenyl; 
 R d  is phenyl; 
 R e  is phenyl; and 
 R f  is phenyl, methyl, p-(OMe)phenyl, or iso-propyl.